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US4314937A - 1:2 Chromium unsymmetrical complexes of azo and disazo dyes - Google Patents

1:2 Chromium unsymmetrical complexes of azo and disazo dyes Download PDF

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Publication number
US4314937A
US4314937A US06/128,228 US12822880A US4314937A US 4314937 A US4314937 A US 4314937A US 12822880 A US12822880 A US 12822880A US 4314937 A US4314937 A US 4314937A
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chromium
parts
group
nitro
dyes
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Fabio Beffa
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BASF Corp
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Ciba Geigy Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/14—Monoazo compounds
    • C09B45/16—Monoazo compounds containing chromium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B45/00—Complex metal compounds of azo dyes
    • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
    • C09B45/24—Disazo or polyazo compounds
    • C09B45/26—Disazo or polyazo compounds containing chromium
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/02—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes
    • D06P1/10—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using azo dyes containing metal

Definitions

  • the present invention provides chromium complex dyes of the formula ##STR2## wherein X 1 represents a hydrogen or halogen atom, a C 1 -C 5 -alkyl group, a C 1 -C 2 -alkoxy group, a nitro group, a C 2 -C 3 -alkanoylamino or C 2 -C 3 -alkoxycarbonylamino group,
  • Me.sup. ⁇ represents a cation
  • Ar represents the radical of an aromatic or heterocyclic diazo component which carries one to three SO 3 H and/or COOH groups, preferably one to three SO 3 H groups or one SO 3 H and one COOH group, and is optionally further substituted by halogen, C 1 -C 5 -alkyl, C 1 -C 2 -alkoxy or nitro.
  • Ar is primarily a naphthalene or benzene ring which carries 1 to 3, preferably 1 or 2, sulpho groups, and is optionally further substituted by chlorine, nitro, C 1 -C 5 -alkyl or C 1 -C 2 -alkoxy.
  • halogen denotes herein fluorine and chiefly chlorine and bromine.
  • novel dyes are obtained by reacting one of the azo dyes of the formula ##STR3## or a disazo dye of the formula ##STR4## with a chromium donor to give the 1:1 chromium complex and subsequently reacting this latter with the non-metallised dye of the formula (3) or (2) to give the 1:2 complex.
  • a chromium donor to give the 1:1 chromium complex
  • the 1:1 chromium complex of the monoazo dye of the formula (2) is prepared and then reacted with the disazo dye of the formula (3).
  • the starting dyes of the formula (2) or (3) can also contain groups from which hydroxyl groups are formed during the chroming, for example low molecular acyloxy or alkoxy groups, in particular methoxy groups.
  • the monoazo dyes can be prepared in conventional manner by coupling a 1-hydroxy- or 1-alkoxy-2-aminonitrobenzene to ⁇ -naphthol.
  • X 1 represents a hydrogen or chlorine atom, a nitro or methyl group.
  • the disazo dyes of the formula (3) are obtained by coupling for example the diazonium compound of an amine Ar--NH 2 with a 1-hydroxy-2-aminobenzene the amino group of which is protected by acylation.
  • the azo dye obtained is then diazotised after liberation of the amino group by saponification and coupled to ⁇ -naphthol.
  • Suitable arylamines of the formula Ar--NH 2 are for example: 2-, 3- or 4-sulphoaniline, aniline-2,4-disulphonic acid, anthranilsulphonic acid, 4-methyl-2- or -3-sulphoaniline, 4-chloro-3-sulphoaniline, 4-nitro-2-sulphoaniline, 4-methoxy-3-sulphoaniline, 2-naphthylamine-6,8-disulphonic acid, 1-naphthylamine-4-, -6- or -7-sulphonic acid, 1-naphthylamine-4,8-disulphonic acid, 1-naphthylamine-3,6,8-trisulphonic acid etc.
  • Heterocyclic amines such as 2-aminobenzthiazole, are also suitable.
  • the conversion of the azo dye of the formula (2) or (3) into the 1:1 chromium complex is carried out by conventional methods which are known per se, for example by reacting it in an acid medium with a salt of trivalent chromium, for example chromium formiate, chromium sulphate, chromium chloride hexahydrate or chromium fluoride, at boiling temperature or, if appropriate, at temperatures exceeding 100° C.
  • Trivalent chromium can also be obtained in the reaction mixture from chromium (VI) compounds, for example chromate, by simultaneously adding a reducing agent.
  • the metallising can be carried out in an aqueous, aqueous-organic or organic medium.
  • reaction of the 1:1 chromium complex of the dye of formula (2) or (3) with a dye of the formula (3) or (2) is advantageously carried out in a neutral to weakly alkaline medium, in an open or closed apparatus, at elevated temperature, for example at temperatures between 50° and 120° C.
  • the process can be carried out in organic solvents, for example alcohols or ketones or in an aqueous solution, in which case, if appropriate, the addition of solvents, for example of alcohols, formamide etc., can promote the reaction. It is usually advisable to react as far as possible equivalent amounts of the chromium-containing 1:1 complex and of the metal-free dye, the molecular ratio between metal-free dye and 1:1 complex advantageously being at least 0.85:1 and at most 1:0.85.
  • the chromium-containing mixed complexes of the present invention which are obtained by the above process are isolated with advantage in the form of their salts, in particular their alkali, for example lithium, salts, above all, sodium salts, or also ammonium salts. They are suitable for dyeing and printing nitrogen-containing material such as wool, silk, synthetic polyamide material and, in particular, for dyeing leather.
  • the dyes containing 1 to 2 sulpho groups are suitable above all for dyeing wool, silk and synthetic polyamide; and the leather dyes can contain 1 to 3 sulpho groups. Black or brownish-black shades of good covering power are obtained in all cases.
  • the dyes give level dyeings with good fastness to light, washing, water, perspiration, alkali, acid, dry cleaning, diffusion, decatizing and rubbing. They reserve well fibres from cotton, viscose cellulose acetate, polyester and polyacrylonitrile. The novel dyes are also suitable for use in mixtures.
  • EXAMPLE 2 ##STR6## 30.9 Parts of the monoazo dye obtained from diazotised 5-nitro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene are suspended in 300 parts by volume of n-butanol. After addition of 26.65 parts of chromium chloride hexahydrate, the mixture is stirred at 110° to 116° C. while the water which forms is separated as an azeotrope. The chroming is complete after approx. 3 to 4 hours. To the dye solution are then added 44.8 parts of the disazo dye obtained from diazotised 3-amino-4-hydroxyazobenzene-3'-sulphonic acid and 2-hydroxynaphthalene and 20 parts of calcined sodium carbonate.
  • the batch is then stirred at 110° to 117° C. until the addition reaction is complete.
  • the reaction mixture is subsequently filtered until clear and evaporated to dryness to yield a black powder which dissolves in water to and dyes wool or polyamide material from a neutral to weakly acid bath in black shades of good fastness properties.
  • EXAMPLE 3 ##STR7## 44.8 Parts of the disazo dye obtained from diazotised 3-amino-4-hydroxyazobenzene-3'-sulphonic acid and 2-hydroxynaphthalene are suspended in 400 parts by volume of n-butanol. After addition of 26.65 parts of chromium chloride hexahydrate, the mixture is stirred while the water which forms is separated as an azeotrope. The chroming is complete after approx. 3 to 4 hours. To the dye solution are then added 30.9 parts of the monoazo dye obtained from diazotised 4-nitro-2-amino-1-hydroxybenzene and 2-hydroxy-naphthalene and 20 parts of calcined sodium carbonate.
  • reaction mixture is then stirred until the addition reaction is complete, subsequently filtered until clear if necessary, and evaporated to dryness to yield a black powder which dissolves in water and colours leather, wool and polyamide material from a weakly acid bath in fast brownish-black shades of good fastness properties.
  • Black and brownish-black dyes with similar properties are obtained by reacting the mono- and disazo dyes as described in Examples 1 to 3 to give asymmetrical 1:2 chromium complexes.
  • 100 parts of clothing velours leather (dry weight) are wet back at 50° C. for 2 hours in a solution of 1000 parts of water and 2 parts of 24% ammonia and subsequently dyed for 1 hour at 60° C. in a solution of 1000 parts of water, 2 parts of 24% ammonia and 6 parts of the dye of Example 1.
  • a solution of 40 parts of water and 4 parts of formic acid (85%) is then added and dyeing is continued for a further 30 minutes.
  • the leather is then thoroughly rinsed and, if appropriate, treated for 30 minutes at 50° C. with 2 parts of a dicyandiamine/formaldehyde condensation product.
  • Other kinds of velour leather as well as glove leather can be dyed black in the same manner.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Coloring (AREA)

Abstract

Chromium complex dyes of the formula ##STR1## wherein represents a halogen atom, a C1 -C5 -alkyl group, a C1 -C2 -alkoxy group, a nitro group, a C2 -C3 -alkanoylamino or C2 -C3 -alkoxycarbonylamino group,
Me⊕ represents a cation, and
Ar represents the radical of an aromatic or heterocyclic diazo component which carries one to three SO3 H and/or COOH groups, preferably one to three SO3 H groups or one SO3 H and one COOH group, and is optionally further substituted by halogen, C1 -C5 -alkyl, C1 -C2 -alkoxy or nitro. These dyes are suitable for dyeing and printing nitrogen-containing material such as wool, silk, synthetic polyamide and especially leather.

Description

This is a continuation-in-part of application Ser. No. 924,316, filed on July 13, 1978, now abandoned, which in turn was a continuation of application Ser. No. 762,062, filed on Jan. 24, 1977, now abandoned.
The present invention provides chromium complex dyes of the formula ##STR2## wherein X1 represents a hydrogen or halogen atom, a C1 -C5 -alkyl group, a C1 -C2 -alkoxy group, a nitro group, a C2 -C3 -alkanoylamino or C2 -C3 -alkoxycarbonylamino group,
Me.sup.⊕ represents a cation, and
Ar represents the radical of an aromatic or heterocyclic diazo component which carries one to three SO3 H and/or COOH groups, preferably one to three SO3 H groups or one SO3 H and one COOH group, and is optionally further substituted by halogen, C1 -C5 -alkyl, C1 -C2 -alkoxy or nitro.
Ar is primarily a naphthalene or benzene ring which carries 1 to 3, preferably 1 or 2, sulpho groups, and is optionally further substituted by chlorine, nitro, C1 -C5 -alkyl or C1 -C2 -alkoxy. The term "halogen" denotes herein fluorine and chiefly chlorine and bromine.
The novel dyes are obtained by reacting one of the azo dyes of the formula ##STR3## or a disazo dye of the formula ##STR4## with a chromium donor to give the 1:1 chromium complex and subsequently reacting this latter with the non-metallised dye of the formula (3) or (2) to give the 1:2 complex. Preferably the 1:1 chromium complex of the monoazo dye of the formula (2) is prepared and then reacted with the disazo dye of the formula (3).
Instead of containing hydroxyl groups, the starting dyes of the formula (2) or (3) can also contain groups from which hydroxyl groups are formed during the chroming, for example low molecular acyloxy or alkoxy groups, in particular methoxy groups.
The monoazo dyes can be prepared in conventional manner by coupling a 1-hydroxy- or 1-alkoxy-2-aminonitrobenzene to β-naphthol. In preferred monoazo compounds of the formula (2), X1 represents a hydrogen or chlorine atom, a nitro or methyl group.
The disazo dyes of the formula (3) are obtained by coupling for example the diazonium compound of an amine Ar--NH2 with a 1-hydroxy-2-aminobenzene the amino group of which is protected by acylation. The azo dye obtained is then diazotised after liberation of the amino group by saponification and coupled to β-naphthol. Suitable arylamines of the formula Ar--NH2 are for example: 2-, 3- or 4-sulphoaniline, aniline-2,4-disulphonic acid, anthranilsulphonic acid, 4-methyl-2- or -3-sulphoaniline, 4-chloro-3-sulphoaniline, 4-nitro-2-sulphoaniline, 4-methoxy-3-sulphoaniline, 2-naphthylamine-6,8-disulphonic acid, 1-naphthylamine-4-, -6- or -7-sulphonic acid, 1-naphthylamine-4,8-disulphonic acid, 1-naphthylamine-3,6,8-trisulphonic acid etc. Heterocyclic amines, such as 2-aminobenzthiazole, are also suitable.
The conversion of the azo dye of the formula (2) or (3) into the 1:1 chromium complex is carried out by conventional methods which are known per se, for example by reacting it in an acid medium with a salt of trivalent chromium, for example chromium formiate, chromium sulphate, chromium chloride hexahydrate or chromium fluoride, at boiling temperature or, if appropriate, at temperatures exceeding 100° C. Trivalent chromium can also be obtained in the reaction mixture from chromium (VI) compounds, for example chromate, by simultaneously adding a reducing agent. The metallising can be carried out in an aqueous, aqueous-organic or organic medium.
The reaction of the 1:1 chromium complex of the dye of formula (2) or (3) with a dye of the formula (3) or (2) is advantageously carried out in a neutral to weakly alkaline medium, in an open or closed apparatus, at elevated temperature, for example at temperatures between 50° and 120° C.
The process can be carried out in organic solvents, for example alcohols or ketones or in an aqueous solution, in which case, if appropriate, the addition of solvents, for example of alcohols, formamide etc., can promote the reaction. It is usually advisable to react as far as possible equivalent amounts of the chromium-containing 1:1 complex and of the metal-free dye, the molecular ratio between metal-free dye and 1:1 complex advantageously being at least 0.85:1 and at most 1:0.85.
The chromium-containing mixed complexes of the present invention which are obtained by the above process are isolated with advantage in the form of their salts, in particular their alkali, for example lithium, salts, above all, sodium salts, or also ammonium salts. They are suitable for dyeing and printing nitrogen-containing material such as wool, silk, synthetic polyamide material and, in particular, for dyeing leather. The dyes containing 1 to 2 sulpho groups are suitable above all for dyeing wool, silk and synthetic polyamide; and the leather dyes can contain 1 to 3 sulpho groups. Black or brownish-black shades of good covering power are obtained in all cases. The dyes give level dyeings with good fastness to light, washing, water, perspiration, alkali, acid, dry cleaning, diffusion, decatizing and rubbing. They reserve well fibres from cotton, viscose cellulose acetate, polyester and polyacrylonitrile. The novel dyes are also suitable for use in mixtures.
The following Examples illustrate the invention, the parts and percentages being by weight unless otherwise indicated.
EXAMPLE 1 ##STR5## 30.9 Parts of the monoazo dye obtained from diazotised 5-nitro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene are stirred with 26.65 parts of chromium chloride hexahydrate in 500 parts by volume of ethylene glycol at 120° to 125° C. until such time as the starting compound has disappeared. To the solution of the 1:1 chromium complex dye are then added 49.8 parts of the disazo dye obtained from diazotised 3-amino-4-hydroxyazobenzene-(1')-naphthalene-6'-sulphonic acid and 2-hydroxynaphthalene and 80 parts by volume of 20% sodium carbonate solution and the mixture is stirred for a further 1 to 2 hours at 80° to 85° C. to effect addition. When the reaction is complete, the asymmetric chromium-containing dye is precipitated by a saturated solution of sodium chloride, filtered off and dried. The product is a black solution and colours wool or polyamide material as well as leather in fast black shades from a weakly acid bath. EXAMPLE 2 ##STR6## 30.9 Parts of the monoazo dye obtained from diazotised 5-nitro-2-amino-1-hydroxybenzene and 2-hydroxynaphthalene are suspended in 300 parts by volume of n-butanol. After addition of 26.65 parts of chromium chloride hexahydrate, the mixture is stirred at 110° to 116° C. while the water which forms is separated as an azeotrope. The chroming is complete after approx. 3 to 4 hours. To the dye solution are then added 44.8 parts of the disazo dye obtained from diazotised 3-amino-4-hydroxyazobenzene-3'-sulphonic acid and 2-hydroxynaphthalene and 20 parts of calcined sodium carbonate. The batch is then stirred at 110° to 117° C. until the addition reaction is complete. The reaction mixture is subsequently filtered until clear and evaporated to dryness to yield a black powder which dissolves in water to and dyes wool or polyamide material from a neutral to weakly acid bath in black shades of good fastness properties. EXAMPLE 3 ##STR7## 44.8 Parts of the disazo dye obtained from diazotised 3-amino-4-hydroxyazobenzene-3'-sulphonic acid and 2-hydroxynaphthalene are suspended in 400 parts by volume of n-butanol. After addition of 26.65 parts of chromium chloride hexahydrate, the mixture is stirred while the water which forms is separated as an azeotrope. The chroming is complete after approx. 3 to 4 hours. To the dye solution are then added 30.9 parts of the monoazo dye obtained from diazotised 4-nitro-2-amino-1-hydroxybenzene and 2-hydroxy-naphthalene and 20 parts of calcined sodium carbonate. The reaction mixture is then stirred until the addition reaction is complete, subsequently filtered until clear if necessary, and evaporated to dryness to yield a black powder which dissolves in water and colours leather, wool and polyamide material from a weakly acid bath in fast brownish-black shades of good fastness properties.
Black and brownish-black dyes with similar properties are obtained by reacting the mono- and disazo dyes as described in Examples 1 to 3 to give asymmetrical 1:2 chromium complexes.
__________________________________________________________________________
No.                                                                       
   Monoazo dye   Disazo dye                                               
__________________________________________________________________________
    ##STR8##                                                              
                  ##STR9##                                                
    ##STR10##                                                             
                  ##STR11##                                               
    ##STR12##                                                             
                  ##STR13##                                               
    ##STR14##                                                             
                  ##STR15##                                               
    ##STR16##                                                             
                  ##STR17##                                               
    ##STR18##                                                             
                  ##STR19##                                               
    ##STR20##                                                             
                  ##STR21##                                               
    ##STR22##                                                             
                  ##STR23##                                               
    ##STR24##                                                             
                  ##STR25##                                               
10.                                                                       
    ##STR26##                                                             
                  ##STR27##                                               
    ##STR28##                                                             
                  ##STR29##                                               
    ##STR30##                                                             
                  ##STR31##                                               
    ##STR32##                                                             
                  ##STR33##                                               
    ##STR34##                                                             
                  ##STR35##                                               
    ##STR36##                                                             
                  ##STR37##                                               
    ##STR38##                                                             
                  ##STR39##                                               
    ##STR40##                                                             
                  ##STR41##                                               
    ##STR42##                                                             
                  ##STR43##                                               
    ##STR44##                                                             
                  ##STR45##                                               
20.                                                                       
    ##STR46##                                                             
                  ##STR47##                                               
    ##STR48##                                                             
                  ##STR49##                                               
    ##STR50##                                                             
                  ##STR51##                                               
    ##STR52##                                                             
                  ##STR53##                                               
    ##STR54##                                                             
                  ##STR55##                                               
    ##STR56##                                                             
                  ##STR57##                                               
    ##STR58##                                                             
                  ##STR59##                                               
    ##STR60##                                                             
                  ##STR61##                                               
    ##STR62##                                                             
                  ##STR63##                                               
    ##STR64##                                                             
                  ##STR65##                                               
30.                                                                       
    ##STR66##                                                             
                  ##STR67##                                               
    ##STR68##                                                             
                  ##STR69##                                               
    ##STR70##                                                             
                  ##STR71##                                               
    ##STR72##                                                             
                  ##STR73##                                               
    ##STR74##                                                             
                  ##STR75##                                               
    ##STR76##                                                             
                  ##STR77##                                               
    ##STR78##                                                             
                  ##STR79##                                               
    ##STR80##                                                             
                  ##STR81##                                               
    ##STR82##                                                             
                  ##STR83##                                               
    ##STR84##                                                             
                  ##STR85##                                               
40.                                                                       
    ##STR86##                                                             
                  ##STR87##                                               
    ##STR88##                                                             
                  ##STR89##                                               
    ##STR90##                                                             
                  ##STR91##                                               
    ##STR92##                                                             
                  ##STR93##                                               
    ##STR94##                                                             
                  ##STR95##                                               
    ##STR96##                                                             
                  ##STR97##                                               
    ##STR98##                                                             
                  ##STR99##                                               
    ##STR100##                                                            
                  ##STR101##                                              
    ##STR102##                                                            
                  ##STR103##                                              
    ##STR104##                                                            
                  ##STR105##                                              
50.                                                                       
    ##STR106##                                                            
                  ##STR107##                                              
    ##STR108##                                                            
                  ##STR109##                                              
    ##STR110##                                                            
                  ##STR111##                                              
    ##STR112##                                                            
                  ##STR113##                                              
    ##STR114##                                                            
                  ##STR115##                                              
    ##STR116##                                                            
                  ##STR117##                                              
    ##STR118##                                                            
                  ##STR119##                                              
    ##STR120##                                                            
                  ##STR121##                                              
    ##STR122##                                                            
                  ##STR123##                                              
    ##STR124##                                                            
                  ##STR125##                                              
60.                                                                       
    ##STR126##                                                            
                  ##STR127##                                              
    ##STR128##                                                            
                  ##STR129##                                              
__________________________________________________________________________
Dyeing Procedure for Wool
100 parts of wool yarn are put at 50° C. into a dyebath which contains 2 parts of the dye of Example 2, 4 parts of ammonium sulphate and 2 parts of a levelling agent in 4000 parts of water. The liquor is brought to the boil in the course of 45 minutes and kept thereat for a further 45 minutes. The goods are then removed from the bath, thoroughly rinsed with cold water and dried. A level black dyeing is obtained.
Dyeing Procedure for Leather
100 parts of clothing velours leather (dry weight) are wet back at 50° C. for 2 hours in a solution of 1000 parts of water and 2 parts of 24% ammonia and subsequently dyed for 1 hour at 60° C. in a solution of 1000 parts of water, 2 parts of 24% ammonia and 6 parts of the dye of Example 1. A solution of 40 parts of water and 4 parts of formic acid (85%) is then added and dyeing is continued for a further 30 minutes. The leather is then thoroughly rinsed and, if appropriate, treated for 30 minutes at 50° C. with 2 parts of a dicyandiamine/formaldehyde condensation product. Other kinds of velour leather as well as glove leather can be dyed black in the same manner.

Claims (3)

I claim:
1. A chromium complex dye of the formula ##STR130## wherein X1 is hydrogen, chloro, nitro or methyl;
Me.sup.⊕ is a cation; and
Ar is phenyl or naphthyl which is substituted by one or two --SO3 H and is further unsubstituted or substituted by C1 -C5 alkyl, C1 -C2 alkoxy, chloro or nitro.
2. A chromium complex dye according to claim 1, wherein X is hydrogen and the NO2 -group is in the para position to the azo group.
3. A chromium complex dye according to claim 1, wherein the NO2 -group is in the ortho position to the oxygen atom and X1 is nitro which is in the para position to the oxygen atom.
US06/128,228 1976-02-04 1980-03-07 1:2 Chromium unsymmetrical complexes of azo and disazo dyes Expired - Lifetime US4314937A (en)

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CH1356/76 1976-02-04
CH135676A CH619977A5 (en) 1976-02-04 1976-02-04

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US4502860A (en) * 1982-07-02 1985-03-05 Ciba-Geigy Corporation Bis-1:2-chromium complexes of disazo dyes, and their preparation and use
US4623606A (en) * 1986-01-24 1986-11-18 Xerox Corporation Toner compositions with negative charge enhancing additives
US5667534A (en) * 1994-12-21 1997-09-16 Ciba-Geigy Corporation Dye mixtures comprising 1:2 chromium complex dyes, and 1:2 chromium complex dyes
US5916722A (en) * 1998-02-05 1999-06-29 Xerox Corporation Toner compositions
US5948583A (en) * 1998-04-13 1999-09-07 Xerox Corp Toner composition and processes thereof
US6420078B1 (en) 2000-12-28 2002-07-16 Xerox Corporation Toner compositions with surface additives
US6566025B1 (en) 2002-01-16 2003-05-20 Xerox Corporation Polymeric particles as external toner additives
US20060019188A1 (en) * 2004-07-26 2006-01-26 Xerox Corporation Toner compositions

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US4502860A (en) * 1982-07-02 1985-03-05 Ciba-Geigy Corporation Bis-1:2-chromium complexes of disazo dyes, and their preparation and use
US4623606A (en) * 1986-01-24 1986-11-18 Xerox Corporation Toner compositions with negative charge enhancing additives
US5667534A (en) * 1994-12-21 1997-09-16 Ciba-Geigy Corporation Dye mixtures comprising 1:2 chromium complex dyes, and 1:2 chromium complex dyes
US5916722A (en) * 1998-02-05 1999-06-29 Xerox Corporation Toner compositions
US5948583A (en) * 1998-04-13 1999-09-07 Xerox Corp Toner composition and processes thereof
US6420078B1 (en) 2000-12-28 2002-07-16 Xerox Corporation Toner compositions with surface additives
US6566025B1 (en) 2002-01-16 2003-05-20 Xerox Corporation Polymeric particles as external toner additives
US20060019188A1 (en) * 2004-07-26 2006-01-26 Xerox Corporation Toner compositions
US7229735B2 (en) 2004-07-26 2007-06-12 Xerox Corporation Toner compositions

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BR7700662A (en) 1977-10-11
FR2340354B1 (en) 1981-01-09
DE2704364C2 (en) 1988-04-14
GB1566327A (en) 1980-04-30
ZA77607B (en) 1977-12-28
DE2704364A1 (en) 1977-08-18
ES455626A1 (en) 1978-01-01
PT66143B (en) 1978-07-06
AR226022A1 (en) 1982-05-31
JPS6112950B2 (en) 1986-04-10
AU511366B2 (en) 1980-08-14
CH619977A5 (en) 1980-10-31
PT66143A (en) 1977-03-01
AU2195577A (en) 1978-08-10
JPS5295742A (en) 1977-08-11
CA1088051A (en) 1980-10-21
FR2340354A1 (en) 1977-09-02

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